New Method Based on Direct Analysis in Real-Time Coupled with Time-of-Flight Mass Spectrometry (DART-ToF-MS) for Investigation of the Miscibility of Polymer Blends

Abstract

The miscibility of a series of binary blends such as polystyrene/poly(methyl methacrylate) (PS/PMMA), polystyrene/poly(vinyl chloride)(PS/PVC), poly(vinyl chloride)/poly(polymethyl methacrylate)(PVC/PMMA) and poly(ethylene-co-vinyl alcohol)/poly(lactide-co-glycolide acid) PEVAL/PLGA with equal ratios and poly(ethylene oxide)/poly(hydroxyl propyl methyl cellulose) (PEO/PHPMC) containing 30 and 70 wt% PEO, which were randomly chosen among the widely systems reported in the literature, was investigated by a new method based on a direct analysis in real-time coupled with time-of-flight mass spectrometry (DART-ToF-MS). To reach this goal these pairs of polymers and copolymers were prepared by solvent casting method. As a first step, the DSC technique was undertaken in this work to highlight the published results on the miscibility of these binary systems. The thermogravimetry analysis (TGA) was used to define the optimum decomposition temperature of these blends programmed for the study of miscibility using the DART-ToF-MS technique. The results obtained by this method based on the comparison of the nature of the fragments resulting from the isothermal decomposition of the blend with those of their pure components have been very effective in demonstrating the character of miscibility of these systems. Indeed, it was found that the PS/PMMA-50 and PS/PVC-50 blends were immiscible, PVC/PMMA-50 and PEVAL/PLGA-50 miscible, and the PEO/PHMC partially miscible. This method, which is rapid and uses a very small amount of sample (1–2 mg) can be extended in its application to other blends whose other methods used have shown their limits due to the intrinsic properties of the polymers involved.

Applications of ambient ionization mass spectrometry in 2022: An annual review

“…Furthermore, laser‐assisted micro‐pyrolysis with FAPA‐MS has been used for the 3D imaging of polymers and polymer additives, enabling the thermal separation of components prior to analysis. 159 DART and DESI have also been utilized in polymer analysis, for the study of the miscibility of polymer blends 160 and the analysis of sequence‐defined polymers, respectively. 161 In recent years, ambient ionization has also been recognized as a powerful tool for the rapid and real‐time study of chemical reactions.…”

Mass spectrometry of polymers: A tutorial review

“…DART‐MS has been applied to characterize chemical compounds in food (Hajslova et al, 2011), forensic samples (Pavlovich et al, 2018), warfare agents (Forbes & Sisco, 2018), and pharmaceuticals (Vaclavik et al, 2014). Applications to synthetic polymers are scarce and so far have been limited to the characterization of low MW standards (Bridoux & Machuron‐Mandard, 2013), differentiation of nylon types (Zughaibi & Steiner, 2020), identification of polyamides in consumer products (Abe et al, 2020), and investigation of the miscibility of polymer blends in films prepared by solvent casting (AlShehri et al, 2022). The DART sources utilized for polymers were coupled to ToF or Orbitrap mass spectrometers, but the source can be attached to most commercially available mass spectrometers (Pavlovich et al, 2018).…”